Microwave Dielectric Ceramics And Method For Manufacturing The Same

ABSTRACT

A method for manufacturing microwave dielectric ceramics has the steps of: mixing multiple A-metal compounds and sintering multiple A-metal compounds between 1350˜1450° C. for 2˜4 hr to make a first component Ba 5+y (Nb 1−k Mn k ) 4 O 15 ; mixing and sintering multiple B-metal compounds to make a second component Ba 1+z Nb 2 O 6 ; and mixing the first component Ba 5+y (Nb 1−k Mn k ) 4 O 15 , the second component Ba 1+z Nb 2 O 6  and at least one sintering aid to make a third component (1−x)Ba 5+y (Nb 1−k Mn k ) 4 O 5 -xBa 1+z Nb 2 O 6 ; wherein x, y, z and k are molar fractions and 0≦x&lt;1, 0&lt;y≦0.3, 0≦z≦0.3, 0≦k≦0.1; and the at least one sintering aid is 0.3˜3 wt %. The microwave dielectric ceramics of (1−x)Ba 5+y (Nb 1−k Mn k ) 4 O 15 -xBa 1+z Nb 2 O 6  have superior microwave properties, low sintering temperature, simple chemical composition and manufacturing requirements applicable to low temperature co-sintered ceramic systems so no re-tooling is required.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to microwave dielectric ceramics and more particularly to microwave dielectric ceramics being sintered at low temperature and having improved microwave properties and a method of producing the same.

2. Description of the Prior Arts

Wireless communications devices comprise both passive and active components, the former in greater quantity that the latter. However, passive components are very expensive and may account for 70% of the cost of the communications device. Furthermore, integrating passive components allows miniaturized and lightweight communications devices. However, passive components generally comprise dielectric ceramics with very high sintering temperatures (in excess of 1300° C.) and electrodes. Therefore, silver or copper cannot be used. The electrodes must either be expensive platinum or silver palladium alloys.

Current research is directed toward microwave dielectric ceramics co-sintered with conductive metals, referred to as low temperature co-sintered ceramics (LTCC), and having the following advantages:

1. Low sintering temperature (less than 1000° C.).

2. Ceramics can be co-sintered with metals such as gold, silver and copper so forming ceramics with low impedance and low dielectric constant loss for lower cost.

3. A manufacture layer of the ceramic is not limited.

4. Resistors, capacitors and inductors are mounted in the ceramics.

5. Low thermal expansion coefficient and water absorption.

Therefore, LTCC is a good material for high-frequency communications components.

LTCC are classified by the major material of the ceramic, and include BaO—TiO₂—Re₂O₃, Bi₂O₃, BaO—TiO₂, MgO—TiO₂, CaO—TiO₂, ZnO—TiO₂, Zn—SnO₂—TiO₂, BaO—WO₃—CuO and CuO—ZrO₂. An agent is added to the LTCC to promote a low melting point glass phase and reduce the sintering temperature of the ceramics. However, the agent can decrease microwave properties of the LTCC.

However, LTCC still has a high sintering temperature so remains costly and a highly energy dependent process.

To overcome the shortcomings, the present invention provides a microwave dielectric ceramics and method for manufacturing the same to mitigate or obviate the aforementioned problems.

SUMMARY OF THE INVENTION

The main objective of the present invention is to provide microwave dielectric ceramics being sintered at low temperature and having improved microwave properties and a manufacturing method thereof.

The manufacturing method of microwave dielectric ceramics comprises steps of: (a) mixing and sintering multiple A-metal compounds to form a first component; (b) mixing and calcining multiple B-metal compounds to form a second component; and (c) mixing and sintering the first and second components with at least one sintering aid to form themicrowave dielectric ceramics.

The step of (a) mixing and sintering multiple A-metal compounds to form a first component is performed between 1250° C. and 1450° C. for two to four hours and the first component is Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅.

The second component is Ba_(1+z)Nb₂O₆.

The dielectric ceramics is (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅-xBa_(1+z)Nb₂O₆; wherein x, y, z and k is a mole fraction and 0≦x≦1, 0<y≦0.3, 0≦z≦0.3, 0≦k≦0.1; and the sintering aid is 0.3 to 3 wt %.

The microwave dielectric ceramics of (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅-xBa_(1+z)Nb₂O₆ have superior microwave properties, low sintering temperature, simple chemical composition and manufacturing requirements applicable to low temperature co-sintered ceramic systems so no re-tooling is required.

Other objectives, advantages and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow diagram showing a manufacturing method of microwave dielectric ceramics in accordance with the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In describing and claiming the present invention, the following terminology will be used according to the definitions hereunder.

As used herein, “liquid phase sintering” refers to a sintering process in which part of multiple powders and at least one sintering aid is blended and melted to produces a viscous glassy liquid. The process accelerates combination rates and decrease porosity to attain a high density sinter

With reference to FIG. 1, the present invention provides a method for manufacturing microwave dielectric ceramics comprising steps of: (a) mixing and sintering multiple A-metal compounds to form a first component; (b) mixing and calcining multiple B-metal compounds to form a second component; and (c) mixing and sintering the first and second components with at least one sintering aid to form the microwave dielectric ceramics.

The step of (a) mixing and sintering multiple A-metal compounds to form a first component is performed between 1350° C. and 1450° C. for two to four hours (2 to 4 hours) to form a first component being Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅.

The A-metal compounds are Barium-carbonate (BaCO₃), Niobium-oxide (Nb₂O₅) and Manganese-oxide (MnO₂). The BaCO₃ may be about 99.9% pure. The Nb₂O₅ be about 99.7% pure. The MnO₂ may be about 99.5% pure.

The A-metal compounds are BaCO₃ (purity 99.9%), Nb₂O₅ (purity 99.7%), MnO₂ (purity 99.5%) and are mixed in correct ratios to form a first mixture of Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅, wherein y and k are molar fractions and 0<y≦0.3 and 0≦k≦0.1.

Deionized water and Yttrium Toughened Zirconia (YTZ) balls are added to the first mixture and mixed for 24 hours, then dried at about 120° C. The first mixture is placed on an alumina crucible for calcining. A heat profile of the sintering is increasing a temperature by 5° C./min until 1150° C. and maintaining said temperature for about 2 hours. X-ray diffraction (XRD) may be used to confirm the mixture has Ba₅Nb₄O₁₅ crystals. Then deionized water and YTZ balls are mixed for 24 hours and dried in 120° C. before being ground, screened and granulated to make a first green. The first green, may be about 10 mm in diameter and about 5 mm in height, is sintered between 1350° C. to 1450° C. for 2 to 4 hours to form the first component being Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅.

In the step of (b), mixing and calcining multiple B-metal compounds may be performed between 1350° C. and 1450° C. for two to four hours (2 to 4 hours) to form the second component being Ba_(1+z)Nb₂O₆.

The B-metal compounds are BaCO₃ (purity 99.9%) and Nb₂O₅ (purity 99.7%), and are mixed in correct ratios to form a second mixture of Ba_(1+z)Nb₂O₆, wherein z is a mole fraction and 0≦z≦0.3.

The BaCO₃ may be 99.9% pure. The Nb₂O₅ may be 99.7% pure.

Deionized water and YTZ balls are added to the second mixture and mixed for 24 hours, then dried at around 120° C. The second mixture is placed on an alumina crucible to proceed with calcining. A heating profile of the sintering is increasing a temperature by 5° C./min until 1150° C. and maintaining said temperature for about 2 hours. XRD may be used to confirm the mixture has BaNb₂O₆ crystals. Then deionized water and YTZ balls are mixed for 24 hours and dried in 120° C. before being ground, screened and granulated to make a second green. The second green, may be about 10 mm in diameter and about 5 mm in height, is sintered between 1350° C. to 1450° C. for two to four hours to form a second component being Ba_(1+z)Nb₂O₆.

In the step of (c), mixing and sintering the first and second components with at least one sintering aid to form a third component, the third component is (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅.xBa_(1+z)Nb₂O₆; wherein x is a molar fraction and 0≦x<1 and the sintering aid is 0.3˜2.8 wt %.

The sintering aid may be selected from the group comprising B₂O₃, B₂O₃—ZnO, B₂O₃—CuO, B₂O₃—BaO BaO—B₂O₃—CuO.

The first and second components and the at least one sintering aid sare prepared as a third mixture. Deionized water and YTZ balls are added to the third mixture, mixed for 8 hours, then dried in 120° C., then are ground, screened and granulated with an uniaxial pressure of one ton to form a third green. The third green, may be about 10 mm in diameter and about 5 mm in height, is sintered between 860° C. to 950° C. for 2 hours to make a third component (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅-xBa_(1+z)Nb₂O₆.

The following examples further illustrate the present invention but are not to be construed as limiting the invention as defined in the claims appended hereto.

(1) Measuring Method

(a) Crystal Size Analysis

A scattering equipment having a refractive index set to 1.96 and absorption set to 1 is used to indirectly measure crystal size by measuring changes in frequency, angle, polarization and scattered light intensity then, using electrodynamics and statistical mechanics analysis to attain information about molecular mechanics and molecular structure.

(b) Percentage Theoretical Density Analysis

The Archimedes method is used to measure density of crystals. The crystal is immersed in deionized water in a vacuum bottle and air is draw out using a vacuum to attain a weight containing water (Wb) and weight in water (Wc). Then, the crystal is dried and measured to attain a dry weight (Wa), wherein the density (D)=Wa/(Wb=Wc). Then, the density (D) is divided by theoretical density (Ba₅Nb₄O₁₅=6.29 gw/cm³) to attain a percentage theoretical density (T.D. %).

(c) Crystal Structure Analysis

Continuous scanning (CS method) is applied at scanning angles from 20° to 60° at a speed of 4°/min and each 0.02° an X-ray diffraction intensity graphic is produced. The X-ray diffraction (XRD) intensity graphics are compared with the Joint Committee on Powder Diffraction Standards (JCPDS) data to decide on the crystal class of the crystal.

(d) Microstructure Observation

The microstructure of the crystal is observed by scanning electron microscopy (SEM, Joel JSM 6360). The sample is ground, polished, dispersed and put into an electrical furnace for heat etching. Conditions of heat etching are 50 to 100° C. for about 0.5 to 2 hours. Next, the sample plates are sputtered with gold.

(d) Measuring Quality Factor (Q*f)

Using the cylindrical frequency resonant cavity method the quality factor (Q*f) and dielectric constant (K) of the ceramics are obtained. A network analyzer (HP8722ES) analysis the ceramics and collocate with a temperature control box (KSON labtester) to measure the resonant frequency at 0° C., 25° C., 50° C. and 85° C. Using, the resonance frequency at 25° C. as a standard (f₂₅), the value of the temperature coefficient of the resonant frequency (τ_(f)) is calculated using the followingformula:

$\tau_{f} = {\frac{1}{f_{25}}\frac{\partial f}{\partial T}}$

EXAMPLE 1 Analysis of the First Component Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅

The A-metal compounds were purified by calcination at 1150° C. calcination temperature (C.T) for 2 hours to rarefy the A-metal compounds and sintered at 1450° C. for 2 to hours to make a first component Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅. Properties of component 1, Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅, are described in the following tables 1 and 2.

TABLE 1 Microwave dielectric properties Ba_(5+y)Nb₄O₁₅ Density ε F Q * f τ_(f) y = 0.01 5.79 38 5.45 21822 37.6 y = 0.02 5.83 40 5.05 39708 52.1 y = 0.03 6.06 40.5 5.08 42195 60.9 y = 0.04 5.92 39.5 5.08 38115 48.5 y = 0.05 6.08 40.5 5.09 30000 66.9 y = 0.1 5.98 39.1 4.92 28723 66

TABLE 2 Microwave dielectric properties Ba₅(Nb_(1−k)Mn_(k))₄O₁₅ Density ε Q * f τ_(f) k = 0 5.94 38 23650 78 k = 0.002 5.79 32 34250 51 k = 0.005 5.83 37 33462 65 K = 0.01 6.06 35.5 22506 45 k = 0.02 5.92 31 6273 42

As seen in tables 1 and 2, the density and the microwave dielectric properties of the first component Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅ raised as the barium content was increased. When y=0.03, the density and the microwave dielectric properties peak. The percent of theoretic density (T.D. %) was above 95% (T.D. %), K=40˜41, Q*f>40000 and τ_(f)=60 ppm/° C. However, adding manganese shows no marked improvement for material properties. However, adding manganese slightly decreased the temperature coefficient of the resonant frequency (τ_(f)), but adding manganese apparently decreased the density, dielectric constant and quality factor. Therefore, Ba_(5.03)Nb₄O₁₅ has the best microwave properties.

Example 2 Low Sintering Temperature of the First Component Ba_(5.03)Nb₄O₁₅

Generally speaking, the sintering aid can be classified into two types, glass with low melting point and metal oxide with low melting point. The glass sintering aids reduce a melting point of the material but simultaneously lower microwave dielectric properties. The metal oxide sintering aids reduce the melting point of the material without lowering microwave dielectric properties. Therefore, the present invention uses metal oxide sintering aids to lower the melting point of the microwave dielectric ceramics.

The metal oxide sintering aids are preferably selected from the group consisting of B₂O₃, CuO, ZnO and V₂O₅. BaO, B₂O₃ and CuO can cause a eutectic mixture, for example, CuO forms a liquid phase BaCu(B₂O₅) at 875° C. Therefore, using the liquid phase BaCu(B₂O₅) and adding metal oxide powder such as B₂O₃—CuO and ZnO—B₂O₃ can lower the sintering temperature (S.T.) to form Ba_(5.03)Nb₄O₁₅. The Ba_(5.03)Nb₄O₁₅ data is described in the following table 3.

TABLE 3 Microwave dielectric properties Composition Sintering aid S.T. Density ε Q * f τ_(f) Ba_(5.03)Nb₄O₁₅ 0.3B₂O₃:0.3ZnO 900° C./2 h 5.986 40.84 9483 65 0.3B₂O₃:0.3CuO 900° C./2 h 6.068 40.69 16674 62 0.3B₂O₃:0.3CuO:1.5BaO 900° C./2 h 6.014 41.1 18953 52 Ba_(5.05)Nb₄O₁₅ 0.3B₂O₃:0.3CuO 900° C./2 h 6.056 40.71 16657 70 0.3B₂O₃:0.3Li₂O 900° C./2 h 5.892 38.02 17498 66 Ba_(5.10)Nb₄O₁₅ 0.3B₂O₃:0.3CuO 900° C./2 h 6.073 41.4 17024 65

According to table 3, when a weight ratio of B₂O₃—CuO is 0.6wt % the microwave dielectric properties peak. Comparing BaO—B₂O₃—CuO and B₂O₃—CuO, BaO—B₂O₃—CuO is preferred over B₂O₃—CuO due to the lower sintering temperature (less than 900° C). Therefore, the weight ratio of Ba_(5.03)Nb₄O₁₅:BaO:B₂O₃:CuO is 1:0.5:0.4:0.2 can attain better microwave dielectric properties (S.T<900° C., K=40˜41, Q*f>18000, τ_(f)˜50 ppm/° C.).

EXAMPLE 3 Different Ba_(1+z)Nb₂O₆ Content to Regulate Temperature Coefficient

Tables 4a and 4b, below, show the sintering temperature and microwave dielectric properties of (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅-xBa_(1+z)Nb₂O₆ at different BaO contents.

TABLE 4a Microwave dielectric properties S.T ε Q * f τ_(f) 0.95Ba_(5.03)Nb₄O₁₅ + 0.05BaNb₂O₆ + 925° C./2 h 37.4 19993 52 0.3 wt % B₂O₃ + 1.5 wt % BaO 0.9Ba_(5.03)Nb₄O₁₅ + 0.1BaNb₂O₆ + 925° C./2 h 40 30768 42 0.3 wt % B₂O₃ + 2.0 wt % BaO 0.84Ba_(5.03)Nb₄O₁₅ + 0.16_(Ba)Nb₂O₆ + 925° C./2 h 39.4 21730 33 0.3 wt % B₂O₃ + 2.5 wt % BaO

TABLE 4b Microwave S.T dielectric properties Dielectric ceramic ° C. ε Q * f τ_(f) 0.95Ba_(5.03)Nb₄O₁₅ + 0.05Ba_(1.1)Nb₂O₆ + 0.3 wt% B₂O₃ + X wt % BaO X = 0.3 925° C./2 h 41.6 11983 44 X = 0.5 925° C./2 h 41.4 13147 47 X = 1.0 925° C./2 h 41.1 13114 45 X = 1.5 925° C./2 h 40.5 25218 47 0.9Ba_(5.03)Nb₄O₁₅ + 0.1Ba_(1.1)Nb₂O₆ + 0.3 wt % B₂O₃ + X wt % BaO X = 0.5 925° C./2 h 41.5 10695 35 X = 1.0 925° C./2 h 41.3 10855 36 X = 1.5 925° C./2 h 40.8 13346 40 X = 2.0 925° C./2 h 41.1 13136 38 X = 2.5 925° C./2 h 36.7 17024 39 0.84Ba_(5.03)Nb₄O₁₅ + 0.16Ba_(1.1)Nb₂O₆ + 0.3 wt % B₂O₃ + X wt % BaO X = 0.3 925° C./2 h 41.9 10459 28 X = 0.5 925° C./2 h 41.7 7094 29 X = 1.0 925° C./2 h 41.6 9485 31 X = 1.5 925° C./2 h 41.4 10428 35 X = 2.0 925° C./2 h 40.1 12990 33 X = 2.5 925° C./2 h 40.3 13232 25

Using Ba_(1+z)Nb₂O₆ and B₂O₃—CuO to decrease temperature coefficient can seriously decrease quality factor therefore, temperature coefficient should decreased using BaO—B₂O₃. Furthermore, adding Ba_(1.1)Nb₂O₆ has the best effect. Adding Ba_(1.1)Nb₂O₆ can decrease temperature coefficient and increase quality factor. When Ba_(1.1)Nb₂O₆ is 0.16 mole % and BaO is 2.6 wt %, the temperature coefficient is at a minimum and the quality factor is at a maximum. Therefore, the best conditions are sintering 0.84 Ba_(5.03)Nb₄O₁₅, 0.16 Ba_(1.1)Nb₂O₆, 0.3 wt % B₂O₃ and 2.5 wt % BaO to obtain following microwave dielectric properties: K=40.3, Q*f=13232, τ_(f)=+²⁵ ppm/° C. and S.T.=925° C./2 h.

Based on the above mentioned, adding oxide into the microwave dielectric ceramics can obtain higher percent of the theoretic density at lower sintering temperature. But, the effect of adding the BaNb₂O₆ increases the percent of the theoretic density very slightly.

Regarding the percentage theoretical density (TD %), adding sintering aid having low melting point can achieve high percentage theoretical density at low sintering temperature. However, adding BaNb₂O₆ does not increase apparently the percentage theoretical density.

Regarding the quality factor, adding BaO can efficiently increase the quality factor of the material and the quality factor has a highest value (Q*f=42195) when the molar fraction is Ba_(5.03)Nb₄O₁₅. In addition, adding sintering aids such as BaO—B₂O₃—CuO can obtain a high the quality factor (Q*f=20592) and low sintering temperature (less than 900° C.). However, adding BaNb₂O₆ can decrease the quality factor (Q*f) of the material so BaO—B₂O₃ is chosen to reduce the sintering temperature. When the sintering aids are BaO and B₂O₃ respectively of 2.5 wt % and 0.3 wt %, the quality factor (Q*f) has the most preferably value (Q*f=33880).

Regarding the dielectric constant (K), the dielectric constant (K) is effected by the percent of the theoretic density in principle. However, adding the sintering aid makes Ba_(5.03)Nb₄O₁₅ gives a preferable percentage of theoretic density at the lower sintering temperature. Moreover, adding the sintering aid only has a little impact on the dielectric constant and the dielectric constant (K) above 40. However, adding BaNb₂O₆ can make the sintering temperature increase. Therefore, the dielectric constant (K) is 39.5 when the sintering temperature is 925° C.

Regarding the temperature coefficient of the resonant frequency (τ_(f)), adding BaNb₂O₆ decreases effectively τ_(f) value and adding Ba_(1.1)Nb₂O₆ decreases τ_(f) value more effectively than adding BaNb₂O₆ does. When the content of Ba_(1.1)Nb₂O₆ is 0.16 mole %, the temperature coefficient of the resonant frequency (τ_(f)) is a minimum (˜25).

The microwave dielectric ceramics of (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅-xBa_(1+z)Nb₂O₆ in accordance with the present invention has superior quality factor at lower sintering temperature (less than 900° C.). Therefore, microwave dielectric ceramics of (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅-xBa_(1+z)Nb₂O₆ is the preferred material.

Even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and features of the invention, the disclosure is illustrative only. Changes may be made in the details, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed. 

1. A microwave dielectric ceramic formed with at least one sintering aid comprising a main component of the formula (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅-xBa_(1+z)Nb₂O₆ wherein x, y, z and k are molar fractions and 0≦x<1, 0<y≦0.3, 0≦z≦0.3, 0≦k≦0.1.
 2. The microwave dielectric ceramic as claimed in claim 1, wherein the sintering aid is selected from the group consisting of B₂O₃, BaO, ZnO, Li₂O and CuO.
 3. The microwave dielectric ceramics as claimed in claim 2, wherein the two sintering aids being B₂O₃ and BaO are implemented, respectively in ratios of 0.3 wt % to 3 wt %.
 4. A method for manufacturing microwave dielectric ceramics, comprising the steps of: (a) mixing and sintering multiple A-metal compounds between 1350˜1450° C. for 2˜4 hr to make a first component Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅; (b) mixing and calcining multiple B-metal compounds to make a second component Ba_(1+z)Nb₂O₆; (c) mixing the first component Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅ and the second component Ba_(1+z)Nb₂O₆ with at least one sintering aid to make a third component (1−x)Ba_(5+y)(Nb_(1−k)Mn_(k))₄O₁₅-xBa_(1+z)Nb₂O₆; wherein x, y, z and k are molar fractions and 0≦x<1, 0<y≦0.3, 0≦z≦0.3, 0≦k≦0.1; and the sintering aid is 0.3˜3 wt %.
 5. The method for manufacturing microwave dielectric ceramic as claimed in 4, wherein the ratio of x:y:z is 0.16:0.03:0.1.
 6. The method for manufacturing microwave dielectric ceramics as claimed in 4, wherein the at least one sintering aid is selected from the group consisting of B₂O₃, BaO, ZnO, Li₂O and CuO.
 7. The method for manufacturing microwave dielectric ceramics as claimed in 5, wherein the at least one sintering aid is selected from the group consisting of B₂O₃, BaO, ZnO, Li₂O and CuO.
 8. The method for manufacturing microwave dielectric ceramics as claimed in 6, wherein two sintering aids are implemented being B₂O₃ and BaO.
 9. The method for manufacturing microwave dielectric ceramics as claimed in 7, wherein two sintering aids are implemented being B₂O₃ and BaO.
 10. The method for manufacturing a microwave dielectric ceramics as claimed in 8, wherein the respective ratios of B₂O₃ and BaO are 0.3 wt % and 2.5 wt %.
 11. The method for manufacturing a microwave dielectric ceramics as claimed in 9, wherein the respective ratios of B₂O₃ and BaO are 0.3 wt % and 2.5 wt %. 